Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
  • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
  • C08J3/128—Polymer particles coated by inorganic and non-macromolecular organic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
  • C08F218/02—Esters of monocarboxylic acids
  • C08F218/04—Vinyl esters
  • C08F218/08—Vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
  • C08L23/0853—Ethylene vinyl acetate copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
  • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
  • H01B3/448—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from other vinyl compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/04—Homopolymers or copolymers of ethene
  • C08J2323/08—Copolymers of ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
  • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
  • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
  • C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
  • C08J2331/04—Homopolymers or copolymers of vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
  • C08J2471/02—Polyalkylene oxides

Definitions

• the present disclosure relates to a resin pellet, a method of manufacturing a resin pellet, gravure ink and a wire coating material.
• EVA Ethylene-vinyl acetate copolymer
• VA vinyl acetate
• the organic solvents for gravure ink include various ones, and among them, toluene is inexpensive, has appropriate drying property at the time of printing, and has high solubility in resins, additives and the like.
• the solubility of EVA in the ester solvents is lower than that in toluene, and it is necessary to increase the content of the constituent unit derived from VA in EVA in order to secure high solubility of EVA.
• the content of the constituent unit derived from VA is increased, the adhesiveness of EVA is also increased, and therefore there is a problem that blocking is likely to occur.
• an antiblocking agent such as an inorganic filler or a fine particle polymer to the surface of the resin pellet has been proposed (see, for example, Patent Document 2).
• a method of adhering an aqueous emulsion including an ethylene-unsaturated ester copolymer and a surfactant to the surface of EVA to reduce the blocking has also been proposed (see, for example, Patent Document 3).
• a pellet with improved blocking an ethylene-based copolymer pellet obtained by blending (a): from 0.01 to 0.5 parts by weight of an unsaturated fatty acid bisamide having a melting point of from 100° C. to 180° C., and (b): from 0.01 to 0.5 parts by weight of a lubricant that has a melting point of from 60° C. to 90° C. and lowers the melting point of (a) by 20° C. or more when used in combination with (a), has been proposed (see, for example, Patent Document 4).
• Patent Document 1 Japanese Patent Application Laid-Open (JP-A) No. 2006-131843
• the blocking can be reduced, but since the inorganic filler is include, the solubility of the resin pellet is insufficient when the resin pellet is dissolved in a solvent, the solution becomes turbid, and a highly transparent ink may not be obtained.
• An object of the present disclosure is to provide a resin pellet in which the blocking is reduced, a method of manufacturing thereof, and gravure ink and a coating material that include the resin pellet.
• Means for solving the above problems include the following aspects.
• a resin pellet including: a pellet-shaped ethylene-vinyl acetate copolymer; a liquid coating agent; and a solid coating agent adhered to at least a portion of surfaces of the ethylene-vinyl acetate copolymer and of the liquid coating agent, wherein the liquid coating agent is a compound including a hydroxyl group, and the solid coating agent is an organic compound.
• a total adhesion amount of the solid coating agent is 1.0 parts by mass or more with respect to 100 parts by mass of the ethylene-vinyl acetate copolymer.
• ⁇ 3> The resin pellet according to any one of ⁇ 1> or ⁇ 2>, wherein a number obtained by dividing a surface adhesion amount, in parts by mass, of the solid coating agent with respect to 100 parts by mass of the ethylene-vinyl acetate copolymer by a total adhesion amount, in parts by mass, of the solid coating agent with respect to 100 parts by mass of the ethylene-vinyl acetate copolymer is from 0.80 to 1.00.
• ⁇ 4> The resin pellet according to any one of ⁇ 1> to ⁇ 3>, wherein the solid coating agent is adhered to at least a portion of the surface of the ethylene-vinyl acetate copolymer via the liquid coating agent.
• ⁇ 5> The resin pellet according to any one of ⁇ 1> to ⁇ 4>, wherein a number obtained by dividing a total adhesion amount, in parts by mass, of the solid coating agent with respect to 100 parts by mass of the ethylene-vinyl acetate copolymer by a number, number/g, of the ethylene-vinyl acetate copolymer per 1 g of the ethylene-vinyl acetate copolymer is 0.037 or more.
• ⁇ 6> The resin pellet according to any one of ⁇ 1> to ⁇ 5>, wherein a content of a constituent unit derived from vinyl acetate in the ethylene-vinyl acetate copolymer, is from more than 40% by mass to 70% by mass.
• ⁇ 7> The resin pellet according to any one of ⁇ 1> to ⁇ 6>, wherein the organic compound includes an amide of a saturated fatty acid or an unsaturated fatty acid.
• ⁇ 8> The resin pellet according to any one of ⁇ 1> to ⁇ 7>, wherein the organic compound includes an unsaturated fatty acid amide.
• ⁇ 9> The resin pellet according to any one of ⁇ 1> to ⁇ 8>, wherein the organic compound includes an unsaturated fatty acid monoamide.
• the liquid coating agent includes at least one selected from the group consisting of a block copolymer with an ethylene oxide chain and a propylene oxide chain, a random copolymer with an ethylene oxide chain and a propylene oxide chain, and diglycerin.
• ⁇ 13> The method of manufacturing the resin pellet according to ⁇ 11> or ⁇ 12>, wherein the aqueous solution in which the liquid coating agent is dissolved and in which the solid coating agent is dispersed is an emulsion.
• a gravure ink including the resin pellet according to any one of ⁇ 1> to ⁇ 10>.
• a wire coating material including the resin pellet according to any one of ⁇ 1> to ⁇ 10>.
• a resin pellet in which the blocking is reduced, a method of manufacturing thereof, and gravure ink and a coating material that include the resin pellet can be provided.
• a numerical range specified by way of using the expression “(from) . . . to . . . ” includes the numerical values before and after the word “to” as the lower limit value and the upper limit value.
• the amount of each component means the total amount of the plural substances unless otherwise specified.
• the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described in a stepwise manner, or may be replaced with the values shown in the Examples.
• an addition amount of a coating agent means a part by mass of the added coating agent with respect to 100 parts by mass of an ethylene-vinyl acetate copolymer.
• a total adhesion amount means a total of a part by mass of the coating agent existing on a surface of the ethylene-vinyl acetate copolymer and inside the ethylene-vinyl acetate copolymer with respect to 100 parts by mass of the ethylene-vinyl acetate copolymer.
• a surface adhesion amount of the coating agent means a parts by mass of the coating agent existing on the surface of the ethylene-vinyl acetate copolymer with respect to 100 parts by mass of the ethylene-vinyl acetate copolymer.
• a resin pellet in the present disclosure includes a pellet-shaped ethylene-vinyl acetate copolymer (hereinafter, also referred to as “EVA”), a liquid coating agent, and a solid coating agent adhered to at least a portion of surfaces of the ethylene-vinyl acetate copolymer and of the liquid coating agent, in which the liquid coating agent is a compound including a hydroxyl group, and the solid coating agent is an organic compound.
• the total adhesion amount of the solid coating agent is preferably 1.0 parts by mass or more with respect to 100 parts by mass of the pellet-shaped EVA.
• the solid coating agent is preferably adhered to at least a portion of the surface of EVA via the liquid coating agent, from the point of reducing the blocking, the total adhesion amount of the solid coating agent is preferably 1.0 parts by mass or more with respect to 100 parts by mass of EVA.
• the resin pellet of the present disclosure includes the pellet-shaped ethylene-vinyl acetate copolymer (EVA), and the solid coating agent is adhered to at least a portion of the surfaces of EVA and of the liquid coating agent.
• EVA ethylene-vinyl acetate copolymer
• the pellet-shaped resin is useful from the viewpoints of ease of removal from the storage location, ease of supply to a molding apparatus, ease of transport, ease of weighing, and the like.
• EVA is a polymer obtained by copolymerizing ethylene and vinyl acetate.
• the content of a constituent unit derived from vinyl acetate included in EVA is preferably from more than 40% by mass to 70% by mass.
• the aforementioned content is preferably 41% by mass or more, more preferably 42% by mass or more, still more preferably 45% by mass or more.
• the aforementioned content is preferably 65% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, particularly preferably 49% by mass or less, and extremely preferably 47% by mass or less.
• the meltmass-flow rate (MFR; JIS K7210:1999, 190° C. and a load of 2160 g) is preferably from 0.1 g/10 min to 300 g/10 min, more preferably from 10 g/10 min to 200 g/10 min, and still more preferably from 50 g/10 min to 150 g/10 min.
• a method of manufacturing EVA is not particularly limited, and EVA can be manufactured by a known method.
• EVA can be obtained by copolymerization of each polymerizable component under high temperature and high pressure, radical copolymerization of each polymerizable component under middle pressure, or the like.
• the ratio of the pellet-shaped EVA in the resin pellet of the resin pellet is preferably from 80% by mass to less than 99% by mass, and more preferably from 85% by mass to 98% by mass.
• the shape of the pellet-shaped EVA is not particularly limited, and examples thereof include a spherical shape, an elliptical spherical shape, a columnar shape, an elliptical columnar shape, a square shape, a rod shape, and an arbitrary combination of these shapes.
• the width and the length are each independently preferably from 0.5 mm to 12 mm, and more preferably from 1 mm to 7 mm.
• the number of the pellet-shaped EVA per 1 g of the resin pellet of the present disclosure is preferably from 1 number/g to 100 number/g, more preferably from 30 number/g to 70 number/g, and still more preferably from 40 number/g to 60 number/g, from the viewpoint of productivity.
• the resin pellet of the present disclosure includes a liquid coating agent being a compound including a hydroxyl group.
• the liquid coating agent has a function of adhering a solid coating agent on at least a portion of the surface of EVA, and the liquid coating agent may be adhered to the surface of EVA or may be included inside EVA.
• the liquid coating agent means a coating agent that is liquid at 25° C.
• the liquid coating agent is preferably a compound including a hydroxyl group with the viscosity at 25° C. of 100 mPa ⁇ s or more.
• the viscosity at 25° C. is a value measured using a B-type viscometer.
• the lower limit of the viscosity of the liquid coating agent at 25° C. is preferably 100 mPa ⁇ s or more, more preferably 300 mPa ⁇ s or more, and still more preferably 600 mPa ⁇ s or more.
• the upper limit of the viscosity of the liquid coating agent at 25° C. is preferably 20000 mPa ⁇ s or less, more preferably 15000 mPa ⁇ s or less, and still more preferably 13000 mPa ⁇ s or less.
• the liquid coating agent may include an alkyleneoxy group, or may include a structure in which one, or two or more alkyleneoxy groups are repeatedly bonded.
• the repetitive structure may be a random structure, or may be a block structure.
• the alkyleneoxy group is a structure in which an oxygen atom is bonded to at least one of the binding sites of an alkyl group, and a structure in which an alkyl group is bonded to an oxygen atom, such as an ester bond, is not classified as the structure including the alkyleneoxy group.
• the liquid coating agent may be a polyhydric alcohol including two or more hydroxyl groups, or may be a polyhydric alcohol including three or more hydroxyl groups.
• the liquid coating agent may be a compound including two or more alkyleneoxy groups or may be a compound including an ethyleneoxy group and an alkyleneoxy group having three or more carbons.
• the liquid coating agent includes at least one specific liquid coating agent selected from the group consisting of a polyalkylene oxide (for example, polyethylene glycol, and polypropylene glycol), a block copolymer with an ethylene oxide chain and a propylene oxide chain, a random copolymer with an ethylene oxide chain and a propylene oxide chain, glycerin, diglycerin, and a silicone oil.
• a polyalkylene oxide for example, polyethylene glycol, and polypropylene glycol
• a block copolymer with an ethylene oxide chain and a propylene oxide chain a random copolymer with an ethylene oxide chain and a propylene oxide chain
• glycerin diglycerin
• silicone oil for example, silicone oil.
• the specific liquid coating agent preferably includes at least one selected from the group consisting of the aforementioned copolymer, glycerin, diglycerin, and a silicone oil, more preferably includes at least one selected from the group consisting of the aforementioned copolymer, diglycerin, and silicone oil, still more preferably includes at least one selected from the group consisting of the aforementioned copolymer and diglycerin, and particularly preferably includes the aforementioned copolymer.
• the liquid coating agent may include or may not include another liquid coating agent other than the specific liquid coating agent.
• the content of the specific liquid coating agent in the liquid coating agent is preferably from 60% by mass to 100% by mass, more preferably from 80% by mass to 100% by mass, and still more preferably from 90% by mass to 100% by mass.
• the viscosity of the compound at 25° C. is preferably from 100 mPa ⁇ s to 20000 mPa ⁇ s, more preferably from 300 mPa ⁇ s to 15000 mPa ⁇ s, and still more preferably from 600 mPa ⁇ s to 13000 mPa ⁇ s.
• the liquid coating agent includes the block copolymer with an ethylene oxide chain and a propylene oxide chain, or the random copolymer with an ethylene oxide chain and a propylene oxide chain
• the block copolymer with a polyethylene oxide chain and a polypropylene oxide chain is preferable
• a triblock copolymer with a polyethylene oxide chain and a polypropylene oxide chain is more preferable
• a triblock copolymer with a polyethylene oxide chain, a polypropylene oxide chain, and a polyethylene oxide chain in this order is still more preferable.
• the content of the ethylene oxide chain in the liquid coating agent is preferably from 20% by mass to 50% by mass, more preferably from 25% by mass to 45% by mass, and still more preferably from 35% by mass to 45% by mass, with respect to the total.
• the content of the propylene oxide chain in the liquid coating agent is preferably from 50% by mass to 80% by mass, more preferably from 55% by mass to 75% by mass, and still more preferably from 55% by mass to 65% by mass, with respect to the total.
• the liquid coating agent includes the silicone oil
• a modified silicone oil in which an organic group has been introduced into a portion of methyl groups in dimethylpolysiloxane is preferable, and a polyether modified silicone oil in which the introduced organic group is a polyether group is more preferable.
• polyether modified silicone oils examples include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (trade name, manufactured by BYK), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, KF-6204, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).
• the total adhesion amount of the liquid coating agent is preferably from 0.001 parts by mass to 3.0 parts by mass, and more preferably from 0.01 parts by mass to 0.30 parts by mass, with respect to 100 parts by mass of the pellet-shaped EVA.
• the resin agent of the present disclosure includes the solid coating agent adhered to at least a portion of surfaces of EVA and of the liquid coating agent.
• the solid coating agent is an organic compound, and the total adhesion amount is preferably 1.0 parts by mass or more with respect to 100 parts by mass of the pellet-shaped EVA.
• the solid coating agent means a coating agent that is solid at 40° C.
• the organic compound preferably includes an amide of a saturated fatty acid or an unsaturated fatty acid, from the viewpoint of solubility in ester solvents, more preferably includes the unsaturated fatty acid amide such as an unsaturated fatty acid monoamide or an unsaturated fatty acid bisamide, and still more preferably includes the unsaturated fatty acid monoamide.
• the total adhesion amount of the unsaturated fatty acid monoamide may be 1.0 parts by mass or more with respect to 100 parts by mass of the pellet-shaped EVA
• the total adhesion amount of the unsaturated fatty acid bisamide may be 1.0 parts by mass or more with respect to 100 parts by mass of the pellet-shaped EVA
• the total adhesion amount of the unsaturated fatty acid monoamide and the unsaturated fatty acid bisamide may be 1.0 parts by mass or more with respect to 100 parts by mass of the pellet-shaped EVA.
• the organic compound may include or may not include another organic compound other than the amide of the saturated fatty acid or the unsaturated fatty acid.
• the content of the amide of the saturated fatty acid or the unsaturated fatty acid in the solid coating agent is preferably from 60% by mass to 100% by mass, more preferably from 80% by mass to 100% by mass, and still more preferably from 90% by mass to 100% by mass.
• Examples of the amide of the saturated fatty acid or the unsaturated fatty acid include a saturated fatty acid monoamide, an unsaturated fatty acid monoamide, a substituted amide, a methylolamide, a saturated fatty acid bisamide, an unsaturated fatty acid bisamide, a fatty acid ester amide, and an aromatic bisamide.
• saturated fatty acid monoamide examples include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, and hydroxystearic acid amide.
• Examples of the unsaturated fatty acid monoamide include oleic acid amide, and erucic acid amide.
• substituted amide examples include N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stealic acid amide, and N-stearyl erucic acid amide.
• methylol amide examples include methylol stearic acid amide.
• saturated fatty acid bisamide examples include methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide, ethylene bishydroxystearic acid amide, ethylene bisbechenic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbechenic acid amide, hexamethylene hydroxystearic acid amide, N, N′-distealyl adipic acid amide, and N, N′-distearyl sebacic acid amide.
• Examples of the unsaturated fatty acid bisamide include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, and N, N′-dioleyl sebacic acid amide.
• fatty acid ester amide examples include stearamide ethyl stearate.
• aromatic bisamide examples include m-xylylene bisstearic acid amide, m-xylylene bishydroxystearic acid amide, and N, N′-distearylisophthalic acid amide.
• amides of the saturated fatty acid or the unsaturated fatty acid one kind may be used alone, or two or more kinds may be used in combination.
• the total adhesion of the solid coating agent is preferably 1.0 parts by mass or more, from the viewpoint of reducing the blocking of the resin pellet, more preferably 1.1 parts by mass or more, still more preferably 1.9 parts by mass or more, and particularly preferably 2.0 parts by mass or more, with respect to 100 parts by mass of the pellet-shaped EVA.
• the total adhesion of the solid coating agent is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, with respect to 100 parts by mass of the pellet-shaped EVA.
• the number obtained by dividing the total adhesion amount (in parts by mass) of the solid coating agent with respect to 100 parts by mass of EVA by the number (number/g) of EVA per 1 g of EVA is preferably 0.020 or more, and more preferably 0.037 or more.
• the aforementioned value is preferably 0.450 or less, and more preferably 0.300 or less.
• the number obtained by dividing the surface adhesion amount (in parts by mass) of the solid coating agent with respect to 100 parts by mass of EVA by the total adhesion amount (in parts by mass) of the solid coating agent with respect to 100 parts by mass of EVA is preferably from 0.80 to 1.00 and more preferably from 0.85 to 1.00.
• each of the aforementioned values corresponds to what the excellent blocking reducing effect of the resin pellet can be obtained even when the total adhesion amount or the surface adhesion amount of the solid coating agent is relatively small.
• each of the aforementioned values corresponds to what the excellent blocking reducing effect of the resin pellet can be obtained even when the total adhesion amount or the surface adhesion amount of the solid coating agent is relatively large.
• the resin pellet of the present disclosure may include another component as necessary.
• other components include pigments, dyes, antioxidants, lubricants, weathering agents, antiblocking agents other than the aforementioned solid coating agent, heat stabilizers, UV stabilizers, flame retardants, and flame retardant aids.
• the resin pellet of the present disclosure may or may not include another component other than the pellet-shaped ethylene-vinyl acetate copolymer, the liquid coating agent or the solid coating agent.
• the resin pellet of the present disclosure may include an inorganic filler to the extent that the effect of the present invention is exhibited. From the viewpoint of obtaining highly transparent gravure ink, it is preferable that the resin pellet of the present disclosure does not include the inorganic filler.
• Examples of the inorganic filler is not particularly limited and examples thereof include a glass fiber, a carbon fiber, silica, alumina, calcium carbonate, silicon carbide, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircone, forsterite, steatite, spinel, mulite, titania, clay, mica, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and a hydrous silicate.
• the method of manufacturing the resin pellet is a method to manufacture the aforementioned resin pellet of the present disclosure, and the method includes a step of adhering the liquid coating agent to at least a portion of the surface of EVA, and a step of adhering the solid coating agent to at least a portion of the surface of EVA.
• the resin pellet adhering the liquid coating agent and the solid coating agent to at least a portion of the surface of EVA is obtained.
• the step of adhering the liquid coating agent may be performed by spraying an aqueous solution including the liquid coating agent to at least a portion of the surface of EVA, or may be performed by immersing EVA in the aqueous solution including the liquid coating agent.
• the concentration of the liquid coating agent in the aqueous solution may correspond to what 0.1 g to 5.0 g of the liquid coating agent is mixed with water to prepare 50 mL of the liquid mixture, or may correspond to what 0.1 g to 3.0 g of the liquid coating agent is mixed with water to prepare 50 mL of the liquid mixture.
• the step of adhering the solid coating agent may be performed by spraying water with the solid coating agent dispersed or an aqueous solution including the solid coating agent to at least a portion of the surface of EVA, may be performed by contacting (for example, immersing) EVA in the water with the solid coating agent dispersed or the aqueous solution, or may be performed by directly contacting the solid coating agent to EVA.
• the addition amount of the solid coating agent may be from 1.0 parts by mass to 20 parts by mass, or may be from 2.0 parts by mass to 15 parts by mass, with respect to 100 parts by mass of EVA in which the solid coating agent is adhered.
• the average particle size of the solid coating agent is 50 ⁇ m or less, more preferably 40 ⁇ m or less, and still more preferably 30 ⁇ m or less. From the viewpoint of handleability of the solid coating agent, the average particle size of the solid coating agent is 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and still more preferably 0.2 ⁇ m or more.
• the average particle size of the solid coating agent can be measured with a laser diffraction type particle size distribution measuring device.
• the average particle size means an average particle size having a cumulative volume of 50%.
• the average particle size of the solid coating agent is a value measured under the following conditions using, for example, “LA-950” manufactured by HORIBA, Ltd., which is a laser diffraction type particle size distribution measuring device.
• the shape of the solid coating agent is not particularly limited, and examples thereof include powdered, powdery, granular, pellet, flaky, lump, scaly, rodlike, filmy, sheet, fibrous and any combination of these shapes.
• the step of adhering the liquid coating agent and the step of adhering the solid coating agent may be performed separately in random order, or may be performed in parallel. From the viewpoint of workability, the step of adhering the liquid coating agent and the step of adhering the solid coating agent are preferably performed in parallel, and more preferably performed by contacting EVA with an aqueous solution in which the liquid coating agent is dissolved and in which the solid coating agent is dispersed.
• the amount of liquid coating agent and the amount of liquid coating agent adhered to the resin pellet can be adjusted respectively by adjusting the concentration of the liquid coating agent in the aqueous solution and the amount of the solid coating agent dispersed in the aqueous solution respectively.
• the aqueous solution in which the liquid coating agent is dissolved and the solid coating agent is dispersed is preferably an emulsion.
• Examples of the method of forming the emulsion include a method in which water, the liquid coating agent and the solid coating agent are mixed, and the prepared liquid mixture is heated, stirred and the like as necessary.
• the liquid coating agent is preferably a block copolymer with an ethylene oxide chain and a propylene oxide chain and a propylene oxide chain, or a random copolymer with an ethylene oxide chain and a propylene oxide chain.
• the ratio (amount of solid coating agent/amount of liquid coating agent) of the amount of the solid coating agent with respect to the amount of the liquid coating agent in the liquid mixture is preferably from 0.5 to 70, more preferably from 1 to 30, and still more preferably from 2.5 to 10.
• the use of the resin pellet of the present disclosure is not particularly limited and for example, the resin pellet is used as a modifier for gravure ink, a main agent or a modifier for a wire coating material, or the like.
• Gravure ink of the present disclosure includes the aforementioned resin pellet of the present disclosure.
• the gravure ink may include a component included in general gravure ink other than the aforementioned resin pellet of the present disclosure, for example, may include a resin component other than the resin pellet, a solvent, colorant, another component, or the like.
• the solvent examples include an aliphatic cyclic hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a glycol ether solvent and the like.
• the solvent one kind may be used alone, or two or more kinds may be used in combination.
• the solvent preferably includes an ester solvent, and examples of the ester solvent include methyl acetate, ethyl acetate, normal propyl acetate, isopropyl acetate, and butyl acetate.
• Examples of the colorant include pigments and dyes.
• antioxidants examples include antioxidants, lubricants, weathering agents, antiblocking agents, heat-resistant stabilizers, UV stabilizers, flame retardants, flame retardant aids, dispersants, antistatic agents, plasticizers, olefin waxes, and surfactants.
• a wire coating material of the present disclosure includes the aforementioned resin pellet of the present disclosure.
• the wire coating material of the present disclosure is a material for protecting a surface of a wire that is a conductor.
• the wire coating material includes a filler, a flame retardant, or the like.
• EVA included in the resin pellets of the present disclosure may include a relatively large amount of the constituent unit derived from vinyl acetate, or for example, the constituent unit that is more than 40% by mass and 70% by mass or less, many fillers can be added to the wire coating material.
• the wire coating material of the present disclosure may include a component included in a conventionally known wire coating material.
• A-1 EVA (constituent unit derived from vinyl acetate; 46% by mass, MFR at 190° C. and a load of 2160 g measured in accordance with JIS K7210: 1999; 100 g/10 min, pellet with width 2 mm and length 5 mm, number per 1 g of pellet-shaped EVA; 50 number/g)
• A-2 EVA (constituent unit derived from vinyl acetate; 60% by mass, MFR at 190° C. and a load of 2160 g measured in accordance with JIS K7210: 1999; 2.75 g/10 min, pellet with width 5 mm and length 10 mm, number per 1 g of pellet-shaped EVA; 4 number/g)
• KF-6020 polyether modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.
• ELA (B) (average particle size 26 ⁇ m) obtained by ethanol-treating commercially available ELA (B) (erucic acid amide, manufactured by Nippon Fine Chemical Co., Ltd., average particle size 64 ⁇ m).
• the method of ethanol treatment is to dissolve commercially available ELA (B) in 98% ethanol and then dry it with dry air (23° C., 30 L/min) for 24 hours.
• ELA (B) (average particle size 17 ⁇ m) that is an emulsion of ELA (B)
• a resin pellet in which the solid coating agent C-1 or C-3 was adhered on the surface of the resin A was prepared by the following procedures (1) to (4).
• Ion-exchanged water and the liquid coating agent B were mixed to prepare 50 mL of a liquid mixture.
• the solid coating agent C-1 or C-3 was added to the resin A coated with the liquid coating agent B, and the solid coating agent C-1 or C-3 was adhered on the surface of the resin A. The excess solid coating agent was removed to produce the resin pellet.
• a resin pellet in which the solid coating agent C-2 was adhered on the surface of the resin A was prepared by the following procedures (1)′ to (4)′.
• the pellet-shaped resin A shown in Table 1 was used as resin pellets of Comparative Examples 1 and 2, respectively.
• a resin pellet was obtained by adhering the solid coating agent C-1 to the pellet-shaped resin A in the same manner as Example 1 except that the liquid coating agent B was not used and the liquid coating agent B was not adhered to the surface of the resin A.
• the polymer component was removed by filtration, and the thus-obtained filtrate was used to quantify the solid coating agent, which is an amide, by gas chromatography. From the result, the total adhesion amount of the solid coating agent with respect to 100 g of EVA was obtained.

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• 2020
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